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EP0263705A2 - L'usage de composition de résine polyester thermoplastique pour UV-absorption - Google Patents

L'usage de composition de résine polyester thermoplastique pour UV-absorption Download PDF

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Publication number
EP0263705A2
EP0263705A2 EP87308908A EP87308908A EP0263705A2 EP 0263705 A2 EP0263705 A2 EP 0263705A2 EP 87308908 A EP87308908 A EP 87308908A EP 87308908 A EP87308908 A EP 87308908A EP 0263705 A2 EP0263705 A2 EP 0263705A2
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EP
European Patent Office
Prior art keywords
group
substituted
acid
naphthalene
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP87308908A
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German (de)
English (en)
Other versions
EP0263705A3 (en
EP0263705B1 (fr
Inventor
Takuji Hirahara
Takashi Nakamura
Yoshiko 201 Haitsu-Amano Aoyama
Shuichi Maeda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Chemical Corp
Original Assignee
Mitsubishi Kasei Corp
Mitsubishi Chemical Industries Ltd
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Publication of EP0263705A2 publication Critical patent/EP0263705A2/fr
Publication of EP0263705A3 publication Critical patent/EP0263705A3/en
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Publication of EP0263705B1 publication Critical patent/EP0263705B1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/12—Esters; Ether-esters of cyclic polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
    • C08K5/092—Polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • C08K5/3417—Five-membered rings condensed with carbocyclic rings

Definitions

  • the present invention relates to thermoplastic polyester resin compositions.
  • polyesters Due to the excellent mechanical properties and chemical specificities of polyesters represented by polyethylene terephthalate, polyesters have been broadly used for fibers, films, etc. Moreover, due to the excellent transparency, the gas-barrier property and the safety and sanitation properties of polyesters, the suitability of polyesters as the material for containers of carbonated-beverage drinks, fruit juice drinks, liquid seasonings, edible oils, liquors and wines has attracted attention in recent years. Still more, from the viewpoint of energy-saving and as a countermeasure for earthquakes, a new use of polyester films has developed. This is to stick a polyester film to windows for screening heat-radiation or for preventing glass scattering.
  • UV light ultraviolet light
  • these containers and films of polyester are excellent in screening UV light up to 320 nm wavelength range, they are almost transparent to UV light or they almost transmit UV light above the longer wavelength range and visible radiation.
  • an edible oil or a liquid seasoning such as sweet sake, dressing, etc.
  • the container is preserved for a few months, there are many cases where the deterioration of the content of the container, for instance, a delicate change of the colour, taste and flavour, occurs gradually according to the preserving conditions although there are specific cases according to the respective foodstuff filled in the container and to the preserving conditions.
  • the deterioration of the content of the container originates in the external causes such as oxygen, heat, light, particularly ultraviolet, microorganisms, etc.
  • the polyester container since it is relatively excellent in oxygen gas-barrier property if it is possible to further improve the ultraviolet screening property of the polyester container, it becomes possible to prevent remarkably the deterioration of the content even for a long term preservation.
  • an ultraviolet absorbing agent is generally used and added to the polyester for this purpose.
  • the ultraviolet, absorbing agent is generally expensive and the adding step is complicated, and moreover, such an ultraviolet absorbing agent is large in sublimation generally and there are many agents of poor in heat-stability, there are cases of causing troubles in the adding step and at the time of mold-processing, and there is a fear of moving the agent to the content of the container in the case where such an agent is used in the foodstuff container and the packaging of foodstuff. Namely, the use of such an ultraviolet absorbing agent is not necessarily favorable.
  • a polyester resin composition comprising a thermoplastic polyester resin and an amount effective in ultraviolet screening of at least one of naphthalenetetracarboxylic acids, acid anhydrides thereof, imides thereof and esters thereof, can sufficiently screen the UV light in the longer wavelength range as well as the UV light in the shorter wavelength range, and on the basis of the finding, the present invention have been attained.
  • thermoplastic polyester resin composition comprising a thermoplastic polyester resin and an amount effective in ultraviolet screening of at least one of naphthalenetetracarboxylic acids, acid anhydrides thereof, imides thereof and esters thereof.
  • thermoplastic polyester resin composition comprising a thermoplastic polyester resin, an amount effective in ultraviolet screening of at least one of naphthalenetetracarboxylic acids, acid anhydrides thereof, imides thereof and esters thereof, and a naphthalenedicarboxylic acid or a derivative thereof of not less than 0.001 part by weight per 100 parts by weight of said thermoplastic polyester resin.
  • thermoplastic polyester resin composition of the first aspect or the second aspect there is provided a container formed from the thermoplastic polyester resin composition of the first aspect or the second aspect.
  • thermoplastic polyester resin composition of the first aspect or the second aspect there is provided a film or sheet formed from the thermoplastic polyester resin composition of the first aspect or the second aspect.
  • a bottle formed from the thermoplastic polyester resin composition of the first aspect or the second aspect.
  • Fig. 1 shows a light transmissivity of the thermoplastic polyester resin compositions obtained in Examples 1 and 3 and Comparative Example 1
  • Fig. 2 shows a light transmissivity of the thermoplastic polyester resin compositions obtained in Example 2 and Comparative Examples 2 and 3.
  • the heart of the present invention lies in a thermoplastic polyester resin composition produced by adding at least one of naphthalenetetracarboxylic acids, the acid anhydrides thereof, the imides thereof and the esters thereof in an amount effective in ultraviolet screening to a thermoplastic polyester resin.
  • a naphthalenetetracarboxylic acid As the compound added to the polyester resin according to the present invention, a naphthalenetetracarboxylic acid, an acid anhydride thereof, an imide thereof or an ester thereof which has a framework composed of a naphthalene-­tetracarboxylic acid moiety is used.
  • naphthalenetetracarboxylic acid naphthalene-­1,4,5,8-tetracarboxylic acid, naphthalene-1,3,5,7-tetracarboxylic acid, naphthalene-1,2,5,6-tetracarboxylic acid, naphthalene-­2,3,6,7-tetracarboxylic acid, naphthalene-1,3,6,8-­tetracarboxylic acid, naphthalene-1,4,6,7-tetracarboxylic acid, naphthalene-1,2,4,5-tetracarboxylic acid, naphthalene-­1,3,4,5-tetracarboxylic acid, naphthalene-1,2,3,4-­tetracarboxylic acid, etc.
  • an acid anhydride of the above-mentioned acids may be used for the purpose of the present invention.
  • an acid anhydride of the above-mentioned acids may be used for the purpose of the present invention.
  • naphthalene-1,4,5,8-tetracarboxylic acid or the acid anhydride thereof is preferable.
  • ester of the naphthalenetetracarboxylic acid various esters may be used, however, an alkyl ester thereof such as methyl ester, ethyl ester, propyl ester, butyl ester, etc. is preferable.
  • tetramethyl naphthalene-­1,4,5,8-tetracarboxylate tetraethyl naphthalene-1,4,5,8-­tetracarboxylate, tetrapropyl naphthalene-1,4,5,8-­ tetracarboxylate, tetrabutyl naphthalene-1,4,5,8-­tetracarboxylate, tetramethyl naphthalene-1,3,5,7-­tetracarboxylate, tetramethyl naphthalene-1,3,6,8-tetra­carboxylate, etc.
  • the carboxyl groups respectively situating the adjacent positions on the naphthalene ring such as in naphthalene-­1,3,6,8-tetracarboxylic acid, may have formed an anhydride ring.
  • a compound having both the anhydride ring and the ester bond such as 3,6-dimethyl ester of naphthalene-tetracarboxylic acid 1,8-anhydride may be used for the purpose of the present invention.
  • any imides of naphthalene-­tetracarboxylic acid may be used, and such an imide can be produced by reacting naphthalene-1,4,5,8-tetracarboxylic acid or an acid derivative thereof with ammonia; an aliphatic aminocarboxylic acid such as glycine, alanine, valine, ⁇ -aminocaproic acid, etc.; an aminoalcohol; an aromatic aminocarboxylic acid such as o-aminobenzoic acid, m-­aminobenzoic acid and p-aminobenzoic acid and a diamine.
  • the imide compound, particularly the diimide compound is excellent in heat-resistance as compared to the afore-mentioned tetracarboxylic acids, the acid anhydrides thereof or the esters thereof, the imide compound, particularly the diimide compound is particularly preferable.
  • diimide compounds of naphthalene-1,4,5,8-tetracarboxylic acid, which are represented by the following formula(1): wherein R1 and R2 may be the same or different from each other and respectively represent hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group of 1 - 10 carbon atoms which may be substituted, an alkenyl group of 2 - 10 carbon atom which may be substituted, an aryl group of 6 - 10 carbon atoms which may be substituted, an aralkyl group of 7 - 10 carbon atoms which may be substituted or an alkylaralkyl group of 8 - 20 carbon atoms which may be substituted;
  • Q represents halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a carboxyl group, a sulfonic acid group or a salt thereof, an alkyl group of 1 - 10
  • naphthalene-1,4,5,8-tetracarboxydiimides represented by the formula (I) in which R1 and R2 respectively represent a carboxyl group or a lower (1 - 4 carbon atoms) alkyl group substituted by hydroxyl group(s) and l is zero are preferable. etc. may be exemplified as the diimide compound of the present invention.
  • the amount of addition of naphthalenetetracarboxylic acid, the acid anhydride thereof, the imide thereof or the ester thereof, which is effective in the ultraviolet screening is generally 0.001 to 20 part by weight per 100 parts by weight of the thermoplastic polyester resin. In the case where the amount of addition is less than 0.001 part by weight, an efficient effect of the ultraviolet screening cannot be obtained even by addition of a suitable amount of the naphthalenedi­carboxylic acid or a derivative thereof described later.
  • the preferable amount of the addition of the naphthalenetetracarboxylic acid, the acid anhydride thereof, the imide thereof or the ester thereof is from 0.005 to 10 parts by weight per 100 parts by weight of the thermoplastic polyester resin.
  • At least one of napthalenedicarboxylic acid derivatives represented by the following formula(II) or formula(III) is preferably used in combination with naphthalenetetracarboxylic acid, the acid anhydride thereof, the imide thereof or the ester thereof.
  • X is an oxygen atom or a group NR5 wherein R5 is the same as the afore-mentioned R1 and R2;
  • R3 and R4 may be the same or different from each other and represent respectively a hydrogen atom, a halogen atom, an alkyl group of 1 - 10 carbon atoms which may be substituted, an alkenyl group of 2 - 10 carbon atoms which may be substituted, an aryl group of 6 - 10 carbon atoms which may be substituted, an aralkyl group of 7 - 10 carbon atoms which may be substituted or an alkylaralkyl group of 8 - ­20 carbon atoms which may be substituted;
  • a and B may be the same or different from each other and represent respectively a halogen atom, a hydroxyl group, an amino group, a nitro group, a cyano group, a sulfonic acid group or a metal salt thereof, a carboxyl group, an alky
  • naphthalenedicarboxylic acid and the derivative thereof represented by the formula (II) or (III)
  • a compound wherein m and n are respectively zero, R3 and R4 are respectively a hydrogen atom or lower (1 - 4 carbon atoms) alkyl group and R5 is a hydrogen atom, a hydroxyl group or an alkyl group of 1 - 4 carbon atoms is preferable.
  • the structural isomers of dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene­dicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,5-­naphthalenedicarboxylic acid or 2,3-naphthalenedicarboxylic acid; the acid anhydrides thereof; the esters thereof; the aromatic ring substituted compounds thereof by halogen, NO2, NH2, CN, SO3H and COOH; the metal salts thereof; and the imides produced by the reaction of one of these naphthalenedicarboxylic acid with ammonia, amine, aminocarboxylic acid and aminoalcohol may be exemplified.
  • dicarboxylic acid such as 2,6-naphthalenedicarboxylic acid, 2,7-naphthalene­dicarboxylic acid, 1,8-naphthalenedicarboxylic acid, 1,5-­naphthalenedicarboxylic acid or 2,3-n
  • naphthalene-2,3-dicarboxylic acid and the derivatives thereof such as the esters of naphthalene-2,3-dicarboxylic acid such as dimethyl ester, diethyl ester, dipropyl ester and dibutyl ester; naphthalene-2,3-dicarboxylic acid anhydride; naphthalene-2,3-dicarboxyimide; naphthalene-2,3-dicarboxy( ⁇ -­carboxymethyl)imide; naphthalene-2,3-dicarboxy( ⁇ -­carboxyethyl)imide; naphthalene-2,3-dicarboxy-(o-carboxyphenyl)­imide;naphthalene-2,3-dicarboxy-(m-carboxyphenyl)imide; naphthalene-2,3-dicarboxy-(p-carboxy
  • the particularly preferable compound of naphthalene­dicarboxylic acids is naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, naphthalene-2,3-­dicarboxylic acid, naphthalene-1,4-dicarboxylic acid or an ester of these dicarboxylic acids, and the lower (1 - 4 carbon atoms) alkyl ester of these dicarboxylic acids.
  • naphthalenedicarboxylic acid or a derivative thereof is used in combination with the afore-mentioned naphthalenetetracarboxylic acid or a derivative thereof
  • an amount of not less than 0.001 part by weight of the naphthalenedicarboxylic acid or the derivative thereof is added to 100 parts by weight of the thermoplastic polyester resin.
  • the amount is less than 0.001 part by weight, the further improvement of the ultraviolet screening is not seen.
  • the preferable amount of addition of the naphthalenedicarboxylic acid or the derivative thereof is from 0.01 to 10 parts by weight.
  • the compound having the framework composed of naphthalenetetracarboxylic acid and the compound having the framework composed of naphthalenedicarboxylic acid may be added in any step of the production of the polyester, and the above-mentioned compounds added in any step before the mold-­processing can develop the effect of the ultraviolet screening as the same extent as above.
  • the compound having the framework composed of naphthalenetetracarboxylic acid and the compound having the framework composed of naphthalenedicarboxylic acid may be added in any step until the molding of the polyester is finished, for instance, before the polycondensation, during the polycondensation, after the polycondensation, in the powdery or granular state of the polyester, during the molding step of the polyester, etc.
  • the thermoplastic polyester in the present invention is the polyester obtained from at least one species of dicarboxylic acid component represented by the aromatic dicarboxylic acid such as terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicarboxylic acid, diphenyl ether dicarboxylic acid, diphenylsulfonedicarboxylic acid, etc., and esters thereof; the cycloaliphatic dicarboxylic acid which is the aromatic ring hydrogenated compound of the above-mentioned aromatic dicarboxylic acid, such as hexahydro­terephthalic acid, and esters thereof; the aliphatic dicarbo­xylic acid such as succinic acid, adipic acid, sebacic acid, azelaic acid, etc., and esters thereof; and the unsaturated dicarboxylic acid such as fumalic acid and 4-carboxycinnamic acid, and esters thereof, and glycol mainly composed of ethylene glycol.
  • thermoplastic polyester in the present invention polyethylene terephthalate is preferable, however, these polyesters may be the product prepared by copolymerizing, as the acid component, the above-­mentioned dicarboxylic acid as the third component other than terephthalic acid in an amount of not more than 20 mol%.
  • this polyester may be the product prepared by copolymerizing, as the glycol component and the third component other than ethylene glycol, an aliphatic glycol such as diethylene glycol, trimethylene glycol, tetramethylene glycol and neopentyl glycol; a cycloaliphatic glycol such as cyclohexane dimethanol; a bisphenol derivative such as 2,2-bis(4 ⁇ - ⁇ -hydroxyethoxyphenyl)propane and bis-(4 ⁇ -­ ⁇ -hydroxyethoxyphenyl)sulfone and further the polyethylene glycol, polytetramethylene glycol represented by the formula: (wherein n is an integer of 1 to 6 and m is an integer of not less than 4) in an amount of not more than 20 mol%, and may be the polyester formed by copolymerizing an oxyacid component such as hydroxybenzoic acid, etc.
  • an aliphatic glycol such as diethylene glycol, trimethylene glycol, tetramethylene glyco
  • the polyester may be produced by copolymerizing a polyfunctional compound not less than trifunctional such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, pyrromellitic acid, etc. and a monofunctional compound such as o-benzoylbenzoic acid.
  • a polyfunctional compound not less than trifunctional such as pentaerythritol, trimethylolpropane, trimellitic acid, trimesic acid, pyrromellitic acid, etc.
  • a monofunctional compound such as o-benzoylbenzoic acid.
  • the material produced by blending the other thermoplastic resin such as polybutylene terephthalate, polyethylene naphthalate, polyester elastomer, polycarbonate, etc. may be used as the polyester according to the present invention.
  • the limiting viscosity of the polyester used in the present invention is not smaller than 0.5, preferably not smaller than 0.6.
  • the viscosity of the polyester is, for instance, in the case of producing a molded hollow article, particularly important in the relationship to the method of molding. Particularly, in the case of obtaining a substantially nonoriented and molded hollow article by a blowing molding method, it is necessary to maintain the fluidity of the molten polyester at a level higher than a predetermined one for the prevention of draw­ down although the level depends on the capacity of the blow moldings, and in that case, the polyester having a limiting viscosity of not smaller than 0.7, preferably not smaller than 0.8 is preferably used.
  • a polymer of a relatively low viscosity as compared to the case of blow molding in the extruding method wherein the film is obtained by stretching uniaxially or biaxially after forming a sheet, and in the injection molding method by which the variously shaped, and molded articles are obtained, a polymer of a relatively low viscosity as compared to the case of blow molding can be used, and in such cases, the polyester having the limiting viscosity of not smaller than 0.5, preferably not smaller than 0.6 is generally used. However, according to the physical properties required to the molded article, a polyester having a higher viscosity is used.
  • the polyester composition according to the present invention may be the material produced by adding a publicly known additive, for instance, stabilizer, mold release agent, antistatic agent, dispersing agent, dyestuff, pigment, etc., in any step of the production of the polyester.
  • a publicly known additive for instance, stabilizer, mold release agent, antistatic agent, dispersing agent, dyestuff, pigment, etc.
  • Such an additive may be added by the so-called method utilizing the master batch concentrates before mold-processing.
  • dyestuff and pigments used in the present invention titanium oxide, carbon black, phthalocyanine blue, phthalocyanine green, ultramarine, cobalt blue, titanium yellow, red iron oxide, burnt-umber, yellow oxide, etc. and heat-resistant and oil-soluble dyestuffs, in the concrete, oil-soluble dyestuffs having the framework composed of perinones moiety, quinophthalones moiety, anthrapyridones moiety, anthraquinones moiety, etc. may be exemplified. Particularly, the dyestuff and pigments having the structure which reacts to the functional group of the polyester and binds to the polyester chain is preferable.
  • the dyestuff and pigment which are highly compatible with the polyester and show a sufficient heat-stability and colour-­tone stability even at the temperature in the production and processing the polyester are selected and added to the polyester.
  • the dyestuff and pigment which do not have any safety and sanitation problems are selected and added to the polyester.
  • the polyester resin composition according to the present invention may be processed into the molded articles as it is, or as occasion demands, the polyester resin composition is subjected to solid phase polymerization in a high vacuum or under an inert gas for the purposes of making the higher polymerization degree, the lower aldehyde and the lower oligomer, and the thus treated composition may be molded. Or else, the composition is subjected to the after-­treatment such as solvent-extraction by xylene and chloroform, and then the thus treated composition may be used.
  • the polyester resin composition may be converted into a so-called master batch which is coloured to a desired colour of a high concentration of from a few times to 100 times, practically to 50 times of the predetermined concentration, and then the thus prepared master batch is diluted with the non-coloured polyester or the another-coloured polyester, or is used to develop another new colour tone.
  • the polyester resin composition developing finally the desired colour tone may be used.
  • thermoplastic polyester resin compositon excellent in the ultraviolet screening according to the present invention is formed into molded articles by melt-­molding. At that time, all the melt-molding methods generally used in polyester are applicable to the thermoplastic polyester resin composition according to the present invention. More concretely, it is possible to obtain a molded hollow article which is excellent in the ultraviolet screening property, gas-barrier property, the toughness and the chemical-­resistane, and has the glass-like transparency with a high class vision by the blowing method such as the ordinary blow molding method, the injection blow molding method, the cold-parison method in which the preliminarily molded material is biaxially stretched after reheating thereof, etc.
  • the blowing method such as the ordinary blow molding method, the injection blow molding method, the cold-parison method in which the preliminarily molded material is biaxially stretched after reheating thereof, etc.
  • the thus produced hollow article is particularly suitable as the container for the seasoning such as soya­bean sauce, sauces, sweet sake, dressing,etc., edible oils, carbonated-beverage drinkings,fruit juice drinkings, sake, wine, cosmetics and medicines.
  • seasoning such as soya­bean sauce, sauces, sweet sake, dressing,etc., edible oils, carbonated-beverage drinkings,fruit juice drinkings, sake, wine, cosmetics and medicines.
  • the polyester resin composition is processed into a uniaxially or biaxially stretched film after once being processed into a sheet by extrusion molding or is processed into a laminated film together with another resin.
  • the thus prepared film is favorably used in particular as the packaging material for general foods, medicines, cosmetics, etc. and further as the material for sticking to window and as the mulching material used in agriculture and horticulture.
  • the polyester resin composition is favorably used as the material for producing variously molded articles by injection-molding.
  • the limiting viscosity of the resin was measured in a mixture of phenol and tetrachloroethane (50:50 by weight) at 30°C and at a concentration of 1.0 g/dl.
  • the transmission rate of UV light of the film was measured while following the ordinary method and using a spectral photometer (made by HITACHI Ltd., model No. 340).
  • the amount of acetaldehyde contained in the resin was measured by a high-sensitivity gaschromatograph after extracting the resin by water for 2 hours at 160°C.
  • the flow rate of an inert gas was shown by the amount of the gas transmitted through the film per unit time (hour) and per unit weight (kg) of the resin after converting into the volume (litre) at 25°C under a pressure of 1 atom.
  • the thus dried composition was molded into a sheet of a thickness of 350 ⁇ m by an extruder wherein the temperatures of cylinder and the nozzle were set at 275°C, the rotation of the screw was set at 40 rpm and the amount of extrusion was set at 80 g/min.
  • the thus produced film showed the respective light transmissivities at 370 nm and 380 nm of 2.8 % and 15.0 %.
  • the chart of the transmissivity of the sheet is shown in Fig. 1.
  • the thus dried resin composition was subjected continuously to injection-molding by an injection-­molding machine (made by TOSHIBA corporation, IS-60B) wherein the temperatures of the cylinder and the nozzle were set at 275°C, the rotation of the screw was set at 100 rpm, the injection time was set at 10 sec and the temperature of water for cooling the metal mold was set at 10°C for injecting the plates of 100 mm in length and width and 2 mm in thickness.
  • an injection-­molding machine made by TOSHIBA corporation, IS-60B
  • Example 2 The same reaction as in Example 1 was carried out except for adding 20 parts of N,N ⁇ -bis( ⁇ -carboxymethyl)­naphthalene-1,4,5,8-tetracarboxydiimide and 100 parts of naphthalene-2,6-dicarboxylic acid instead of the dianhydride of naphthalene-1,4,5,8-tetracarboxylic acid in Example 1 to obtain a transparent polyester composition of a limiting viscosity of 0.66.
  • the light transmissivity of the sheet of 350 ⁇ m in thickness obtained by molding the thus produced polyester composition was 0.0 % at 370 nm and 0.1 % at 380 nm.
  • the chart of the transmissivity of the sheet is shown in Fig. 2.
  • Example 2 The same reaction as in Example 2 was repeated except for further adding 1.4 part of copper phthalocyanine and 2 parts of a reactive dyestuff of quinophthalones (made by MITSUBISHI Chemical Industries Ltd.) and as a result, a green coloured transparent polyester composition of a limiting viscosity of 0.60 was obtained.
  • the light transmissivity of a sheet of 350 ⁇ m in thickness obtained by molding the thus produced polyester composition in the same manner as in Example 1 was 0.1 % at 370 nm.
  • the chart of the transmissivity of the film is shown in Fig. 1.
  • the thus treated chips were transferred to a stationary-bed solid-phase polymerization column and after drying the chips for 3 hours at from 120 to 160°C under a flow of nitrogen gas of a flow rate of 30 litres/kg ⁇ hour, the thus dried chips were subjected to solid phase polymerization for 10 hours at the resin temperature of 210°C.
  • the limiting viscosity of the thus polymerized material in the solid phase was 0.76, and the material contained 3.1 ppm of acetaldehyde in the chip-form.
  • preforms were molded by an injection-molding machine (made by TOSHIBA Corporation, IS-60) wherein the temperature of the cylinder and the nozzle were set at 275°C, the rotation of the screw was set at 100 rpm, the injection time was set at 10 sec. and the temperature of water for cooling the metal mold was set at 10°C.
  • a blow-molding machine made by Corpoplast Corp., BMB-3 wherein the temperature of pre­heating furnace was set at 90°C, the blow pressure was set at 20 kg/cm2 and the molding cycle was set at 10 sec, a bottle of 1 litre in capacity was obtained.
  • the UV light transmissivity of the part of the bottle of 350 ⁇ m in thickness was 0.1 % at 370 nm and 380 nm.
  • Example 2 Under the same conditions as in Example 1 while only adding 20 parts of germanium dioxide and 20 parts of ortho-phosphoric acid, a polyester composition of a limi­ting viscosity of 0.68 was obtained.
  • the UV light transmissivity of the thus produced sheet was 0.0 % at 370 nm and 0.1 % at 380 nm.
  • Example 2 In the same manner as in Example 1 except for adding 30 parts of naphthalene-1,3,5,7-tetracarboxylic acid instead of 25 parts of dianhydride of naphthalene-1,4,5,8-­tetracarboxylic acid in Example 1, a transparent polyester composition of a limiting viscosity of 0.67 was obtained.
  • the UV light transmissivity of a film of 350 ⁇ m in thickness, which was prepared from the above-mentioned composition was 2.6 % at 370 nm and 15.2 % at 380 nm. While using the above-­mentioned polyester composition, plates of 100 mm in length and width and 2 mm in thickness were injected, however, even after injecting 500 plates, any adhered materials such as white powder were not observed on the thus injected plates.
  • the UV light transmissivity of the thus molded sheet was 2.2 % at 370 nm and 15.8 % at 380 nm.
  • the chart of transmissivity of the sheet is shown in Fig. 2.
  • Table 1 shows the results of Examples 1 to 7 and Comparative Examples 1 to 4 collectively.

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  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP87308908A 1986-10-07 1987-10-07 L'usage de composition de résine polyester thermoplastique pour UV-absorption Expired - Lifetime EP0263705B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP23868686 1986-10-07
JP238686/86 1986-10-07

Publications (3)

Publication Number Publication Date
EP0263705A2 true EP0263705A2 (fr) 1988-04-13
EP0263705A3 EP0263705A3 (en) 1988-08-17
EP0263705B1 EP0263705B1 (fr) 1993-06-30

Family

ID=17033793

Family Applications (1)

Application Number Title Priority Date Filing Date
EP87308908A Expired - Lifetime EP0263705B1 (fr) 1986-10-07 1987-10-07 L'usage de composition de résine polyester thermoplastique pour UV-absorption

Country Status (5)

Country Link
US (1) US4814366A (fr)
EP (1) EP0263705B1 (fr)
JP (1) JPH07116352B2 (fr)
KR (1) KR950011905B1 (fr)
DE (1) DE3786387T2 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002040479A1 (fr) * 2000-11-14 2002-05-23 Shionogi & Co., Ltd. Agents de traitement des infections a helicobacter
WO2003095453A1 (fr) * 2002-05-13 2003-11-20 Shionogi & Co., Ltd. Composes a activite antihelicobacter
US7714044B2 (en) 2003-11-14 2010-05-11 Basf Akitengesellschaft Use of 4-cyano-naphthalene-1, 8-dicarboximide derivatives and related compounds to protect organic material from the damaging effects of light
US8383656B2 (en) 2009-10-09 2013-02-26 The Ohio State University Research Foundation Thiazolidinedione energy restriction-mimetic agents
US10406196B2 (en) 2010-10-19 2019-09-10 K.L.R.M., Llc Compositions and methods for treating, inhibiting the onset, and slowing the progression of erectile dysfunction including naturally occurring age related erectile dysfunction

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EP0335595B1 (fr) * 1988-03-29 1994-06-08 Mitsubishi Kasei Corporation Composition de résine de polyester thermoplastique et articles moulés préparés à partir de cette composition
JPH0717824B2 (ja) * 1988-04-20 1995-03-01 帝人株式会社 樹脂組成物
JPH02223582A (ja) * 1989-02-27 1990-09-05 Mitsubishi Kasei Corp ナフタレンテトラカルボン酸ジイミド化合物
US5001178A (en) * 1989-03-06 1991-03-19 General Electric Company Thermoplastic molding compositions
US5243021A (en) * 1991-07-17 1993-09-07 Lever Brothers Company, Division Of Conopco, Inc. Water-dispersible copolymer containing UVA and UVB light-absorbing monomers
US5134223A (en) * 1991-07-17 1992-07-28 Lever Brothers Company, Division Of Conopco, Inc. Water dispersible or water soluble copolymer containing UV-absorbing monomer
US5290835A (en) * 1991-10-01 1994-03-01 Teijin Limited Electrical and electronic parts formed of polybutylene naphthalenedicarboxylate
US5482986A (en) * 1993-07-22 1996-01-09 Mitsui Toatsu Chemicals, Inc. Benzopyran compound and use of the same
CN1127543C (zh) * 1998-12-14 2003-11-12 新光合成纤维股份有限公司 阻光性聚酯组合物，阻光性聚酯纤维和由其制得的布种及物品
US6417255B1 (en) * 1999-12-15 2002-07-09 General Electric Company High performance thermoplastic compositions with improved melt flow behavior
ATE514733T1 (de) * 2002-08-30 2011-07-15 Basf Se Verfahren zur herstellung von gefärbtem kunststoff oder polymeren farbpartikeln
CN100558814C (zh) * 2002-09-09 2009-11-11 索尼株式会社 树脂组合物
US20040185196A1 (en) * 2003-03-21 2004-09-23 Yu Shi Packaged potable liquid with UV absorber for reduced off-taste from closure and method
ES2321307T3 (es) * 2003-11-14 2009-06-04 Basf Se Uso de derivados de 4-ciano-neftaleno-1,8-dicarboximida y compuestos relacionados para proteger material organico de los dañinos de la luz.
JP5063935B2 (ja) * 2006-06-02 2012-10-31 東洋製罐株式会社 燃料電池カートリッジ用ポリエステル製容器
KR101691267B1 (ko) * 2011-09-12 2016-12-29 프라스틱팩 팩키징, 인코퍼레이티드 단층 이산화탄소 장벽 페트병
GB201317705D0 (en) * 2013-10-07 2013-11-20 Dupont Teijin Films Us Ltd Copolyesters
US11760072B2 (en) * 2017-10-03 2023-09-19 Toray Industries, Inc. Laminate film

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GB728550A (en) * 1952-09-04 1955-04-20 Wingfoot Corp Polyesters
US2912442A (en) * 1956-11-23 1959-11-10 Du Pont 2, 3, 6, 7 naphthalenetetracarboxylic acid and its functional derivatives
US3052636A (en) * 1959-05-26 1962-09-04 Gen Aniline & Film Corp Ultra-violet light stabilized organic compositions
NL124226C (fr) * 1962-06-15
US3239363A (en) * 1962-10-05 1966-03-08 Marathon Oil Co Esters of isomeric dicarboxynaphthalenes
US3386795A (en) * 1964-10-05 1968-06-04 Eastman Kodak Co Polyesters having improved dyeing properties
GB1124536A (en) * 1966-07-01 1968-08-21 Ici Ltd Polycyclic dyestuffs derived from a substituted naphthalene-1:4:5:8-tetracarboxylic acid
GB1147232A (en) * 1966-07-01 1969-04-02 Ici Ltd Naphthalene-1:4:5:8-tetracarboxylic acid diimide derivatives
GB1239751A (fr) * 1967-05-23 1971-07-21
JPS4832421B1 (fr) * 1970-04-02 1973-10-05
US3755152A (en) * 1970-09-14 1973-08-28 Ouvoe Chem Ind Inc Removing contaminants from organic materials
JPS5027109B2 (fr) * 1972-07-05 1975-09-05
US3954840A (en) * 1973-02-14 1976-05-04 Teijin Ltd. 1,3,5,7-Naphthalenetetracarboxylic acids and process for preparation thereof
JPS5398242A (en) * 1977-01-31 1978-08-28 Nippon Carbide Kogyo Kk Roottvegetavle cultivating method and covering material therefor
JPS53124556A (en) * 1977-04-07 1978-10-31 Nippon Carbide Ind Co Ltd Transparent multilayer film
SU703612A1 (ru) * 1977-04-15 1979-12-15 Предприятие П/Я М-5400 Способ получени окрашенного поликапроамида
EP0156966B1 (fr) * 1981-07-20 1988-10-19 Teijin Limited Composition de polyester entièrement aromatique et procédé pour sa fabrication
JPH07102442B2 (ja) * 1991-12-10 1995-11-08 株式会社中村金属工業所 パイプ鋳ぐるみ鋳造法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002040479A1 (fr) * 2000-11-14 2002-05-23 Shionogi & Co., Ltd. Agents de traitement des infections a helicobacter
WO2003095453A1 (fr) * 2002-05-13 2003-11-20 Shionogi & Co., Ltd. Composes a activite antihelicobacter
US7714044B2 (en) 2003-11-14 2010-05-11 Basf Akitengesellschaft Use of 4-cyano-naphthalene-1, 8-dicarboximide derivatives and related compounds to protect organic material from the damaging effects of light
CN1902180B (zh) * 2003-11-14 2010-08-25 巴斯福股份公司 4-氰基-萘-1,8-二甲酰亚胺衍生物和相关化合物在保护有机材料使之防止受到光的损害影响中的用途
US8383656B2 (en) 2009-10-09 2013-02-26 The Ohio State University Research Foundation Thiazolidinedione energy restriction-mimetic agents
US10406196B2 (en) 2010-10-19 2019-09-10 K.L.R.M., Llc Compositions and methods for treating, inhibiting the onset, and slowing the progression of erectile dysfunction including naturally occurring age related erectile dysfunction

Also Published As

Publication number Publication date
KR950011905B1 (ko) 1995-10-12
US4814366A (en) 1989-03-21
JPS63225650A (ja) 1988-09-20
KR880005208A (ko) 1988-06-28
EP0263705A3 (en) 1988-08-17
EP0263705B1 (fr) 1993-06-30
DE3786387D1 (de) 1993-08-05
JPH07116352B2 (ja) 1995-12-13
DE3786387T2 (de) 1993-10-14

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